Disazo dyestuffs

ABSTRACT

DIAZO DYESTUFF CONTAINING 1 SULPHONIC ACID GROUP OF THE GENERAL FORMULA 1-(((R1)M-PHENYL)-N=N-),4-((2-R4,4-(PHENYL-CH2-N(-CH2CH2-SO3H)-),5-R5 -PHENYL)-N=N-),R2,R3-BENZENE WHEREN R1 REPRESENTS HYDROGEN, CHLORINE, BROMINE OR A METHYL, ETHYL OR TRIFLUOROMETHYL GROUP R2 AND R3 DENOTE HYDROGEN OR INDEPENDENTLY OF ONE ANOTHER DENOTE CHLORINE, BROMINE OR A METHYL, ETHYL METHOXY OR ETHOXY GROUP, R4 REPRESENTS HYDROGEN, CHLORINE, BROMINE OR A METHYL ETHYL, METHOXY OR ETHOXY GROUP OR THE RESIDUE NHCOCNH2N+1, WITH N REPRESENTING A NUMBER FROM O TO 4, R5 DENOTED HYDROGEN OR A METHYL, MEHOXY OR ETHOXY GROUP, AND M REPRESENTS AN INTEGER FROM 1 TO 5.

United States Patent 3,709,870 DISAZO DYESTUFFS Gerhard Wolfrum, Leverkusen, Germany, assignor to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany No Drawing. Filed June 4, 1970, Ser. No. 43,581 Claims priority, application Germany, June 13, 1969, P 19 30 261.5 Int. Cl. C07c 107/06; C09b 31/04 US. Cl. 260-186 3 Claims ABSTRACT OF THE DISCLOSURE Disazo dyestuffs, containing 1 sulphonic acid group, of the general formula R represents hydrogen, chlorine, bromine or a methyl,

ethyl or trifiuoromethyl group,

R and R denote hydrogen or independently of one another denote chlorine, bromine or a methyl, ethyl, methoxy or ethoxy group,

R represents hydrogen, chlorine, bromine or a methyl, ethyl, methoxy or ethoXy group or the residue NHCOC H with n representing a number from 0 to 4,

R denotes hydrogen or a methyl, methoxy or ethoxy group, and

m represents an integer from 1 to 5.

The new dyestuffs are especially suitable for the dyeing of nitrogen-containing materials. They are very well ab sorbed on polyatnide fibers from acid and neutral dyebaths.

The subject of the invention is new disazo dyestulfs, containing 1 sulphonic acid group, of the formula (I) processes for their manufacture and their use for dyeing nitrogen-containing fiber materials.

In general Formula I,

R represents hydrogen, chlorine, bromine or a methyl,

ethyl or trifiuoromethyl group,

R and R;,, which may be identical or different from one another, represent hydrogen, chlorine, bromine, or a methyl, ethyl, methoxy or ethoxy group,

R represents hydrogen, chlorine, bromine, a methyl, ethyl, methoxy or ethoxy group or the residue NHCOC H (m=04),

R represents hydrogen, or a methyl, methoxy or ethoxy group, and

m denotes an integer from 1-5.

A particularly valuable group of dyestuffs within the framework of Formula I corresponds to the formula 3,709,870 Patented Jan. 9, 1973 "ice wherein R R and R independently of one another represent hydrogen or a methyl or ethyl group.

A very particularly valuable compound within the framework of the new dyestuffs of Formula I corresponds to the formula 0 H2 0 HzS 0 H GHQ a The new disazo dyestuffs (I) are manufactured by diazotising amines of formula (R1) in (II) wherein R and m have the above-mentioned significance, and coupling with amines of Formula III or their derivatives (IV) or (V) which are protected in the amino group,

wherein R and R have the above-mentioned significance. The monoazo dyestufls of formula obtainable in this way, wherein R R R and m have the above-mentioned significance, are diazotisedwhere appropriate after liberating the amino group by acid or alkaline saponification if coupling components (IV) or (V) are usedand coupled with an amine of formula (VII) benzene, 3-aminoethylbenzene, 3-chloraniline, 3-bromaniline, Z-aminoanisole, B-aminoanisole, Z-amino-ethoxybenzene, S-amino-ethoxybenzene, 1-amino-2,5-dimethylbenzene, 1amino-2,3-dimethylbenzene, 1-amino-3,5-dimethylbenzene, 3-amino-4-methoxy-toluene, 2-amino-4- methoxy-toluene, Z-amino-1,4-dimethoxybenzene, 2-amino-4-ethoxy-toluene and Z-amino-1,4 diethoxybenzene.

Amines of the Formula III which easily form diazoamino compounds instead of azo compounds with diazonium compounds, can also be employed for the coupling in the form or their N-sulphonic acids (IV) or w-methanesulphonic acids (V).

End components of Formula V11 are for example:

N-benzyl-N- (/8-sulphoethyl) -aniline,

3- [N-benzyl-N- (fi-sulphoethyl) -amino] -toluene,

3- [N-benzyl-N- fl-sulphoethyl) -amino] -ethylbenzene,

3- [N-benzyl-N- fi-sulphoethyl -amino -chlorobenzene,

3 [N-benzyl-N-( fi-suphoethyl -amino] -bromobenzene,

3- [N-benzyl-N- (fi-sulphoethyl -amino] -anisole,

3- [N-benzyl-N- fi-sulphoethyl) -amino] -ethoxybenzene,

3 [N-benzyl- (fi-sulphoethyl -amino] -formanilide,

3 [N-b enzyl-N- B-sulphoethyl -amino] -acetanilide,

3- N-benzyl-N- (,s-sulphoethyl) -amino] -propionic acid anilide,

4-acetylarm'no-2- [N-benzyl-N- (fl-sulphoethyl) -amino] toluene,

4-acetylamino-2- [N-benzyl-N- (fi-sulphoethyl) -amino] anisole,

4-acetylamino-2- [N-benzyl-N- B-sulphoethyl -amino] ethoxybenzene,

4-formylamino-2- [N-benzyl-N-(fl-sulphoethyl) -amino]- anisole,

4-propionylamino-2- {N-benzyl-N- B-sulphoethyl) amino] -anisole,

2- N-benzyl-N- (p-sulphoethyl) -amino] -1,4-dimethoxybenzene, and

2- [N-benzyl-N- (,B-sulphoethyl) -amino] 1,4-diethoxybenzene.

The diazo components of Formula II are diazotised in a known manner, for example in acid, aqueous solution with sodium nitrite solution at -5 C., and combined with the coupling components of Formulae III, IV or V. The coupling can for example be carried out in a neutral to strongly acid pH range in aqueous or organic-aqueous medium. The aminoazo dyestufis (VI) obtainable in this way are water-insoluble and are therefore easy to isolate and obtainable in the pure form. If the amines IV) or (V) are employed as coupling components, the water-insoluble aminoazo dyestuffs (VI) are easily obtained by acid or alkaline saponification.

The further diazotisation of the aminoazo dyestuffs (VI) can for example take place in acid, aqueous dispersion with sodium nitrite solution or in concentrated sulphuric acid or concentrated phosphoric acid with nitrosylsulphuric acid. The diazotisation temperatures can be between 0 C. and 30 C. The coupling with the end components (VII) to give the disazo dyestufis (I) also takes place in a manner which is in itself known, for example in neutral, weakly acid or strongly acid, aqueous medium or also in an aqueous-organic medium. The disazo dyestuffs of Formula I are mostly very sparingly soluble in an acid medium and can therefore be isolated by a simple filtering-off. If the dyestuffs are obtained in an impure form, they can be recrystallised in the usual manner from hot water, optionally with the addition of alkalis. The dyestuffs (I) can be quantitatively separated out from alkaline solution by adding salt. The sparingly water-soluble dyestuffs (I) isolated under acid conditions can be easily rendered water-soluble by, for example, mixing them with salts of strong bases and weak acids, for example trisodium phosphate, disodium hydrogen phosphate, sodium tetraborate, sodium metaphosphate, sodium metasilicate. sodium carbonate and the like.

The dyestulfs of Formula I are suitable for dyeing nitrogen-containing materials such as wool and silk, but preferably synthetic polyamide and polyurethane fiber, in clear color shades having very good general fastness properties.

The dyestuffs are very well absorbed on polyamide fiber both from an acid dyebath and also from a new tral dyebath.

In the examples which follow the parts denote parts by weight and the percentages denote percentages by weight.

EXAMPLE 1 197 parts of 4-aminoazobenzene are finely powdered and introduced at room temperature, whilst stirring, into 1200 parts of 8% strength hydrochloric acid. The suspension thus produced is stirred for some hours. 69 parts of sodium nitrite dissolved in 250 parts of water are then added dropwise at 5-15 C. The diazonium salt solution thus manufactured is freed of a little insoluble matter by filtration and is then added to a solution, adjusted to pH=4-5, of 308 parts of 3-[N-benzyl-N-(fi-sulphoethynamino]-toluene in 2500 parts of water. A pH-value of 4-5 is maintained during the coupling by simultaneous addition of sodium hydroxide solution. After completion of coupling, the dyestutf is filtered otf, washed once or twice with water and dried.

515 parts of dyestulf of formula CHaCHrSDaH a. 3 are obtained.

10.7 parts of Z-aminotoluene are diazotised in the usual manner and coupled with 10.7 parts of 3-aminotoluene in a weakly acid, aqueous solution to give the dyestufl of formula l CH; C

22.5 parts of this aminoazo dyestulf are stirred for several hours in 200 parts of 8% strength hydrochloric acid and are then diazotised at 5-20 C. with a solution of 6.9 parts of sodium nitrite in 30 parts of water. The clear diazom'um salt solution is combined at pH 4-5 with a solution of 31 parts of 3-[N-benzyl-N- (B-sulphoethyD-amino]-tolnene in 250 parts of water. During the coupling the pH-value is kept at 4-5 by dropwise addition of sodium hydroxide solution. After completion of coupling, the disazo dyestud of formula is filtered 0E, washed with 2% strength sodium chloride solution and dried. 58 parts of a dark brown powder which dyes polyamide, fiber from acid or neutral liquor in a yellowish-tinged red are obtained.

EXAMPLE 3 10.7 parts of Z-aminotoluene are diazotised in the usual manner and combined in a neutral to weakly acid solution with 20.1 parts of the compound of formula QNH-CHZ-S 0311 After completion of coupling, the mixture is rendered alkaline by adding 200 parts of strength sodium hydroxide solution and the alkaline solution is thereafter heated to the boil for 30 minutes. After cooling, the aminoazo dyestuif of formula Ha a is filtered off, washed with water until neutral and stirred for several hours at room temperature in 200 parts of 8% CHzCHzSOgH is filtered off, washed with 2% strength sodium chloride solution and dried. The dyestutf dyes polyamide filaments from acid and neutral baths in yellowish-tinged red shades.

The table which follows quotes further dyestuffs obtained according to the invention, which dye polyamide filaments in the shades indicated:

Construction Shade on perlon /CHnCH2 S 0 H Yellowish-tlnged red.

/CH:CH:S 0 H D0. & e Q

Ha Hg /CH2CH2S OaH DO. i 5 Q CH CH D0.

/C H2 C H2 S 0 H H N=N N=NN\ (a (s Q /CH:CH2S OaH Red.

CH (ill 33H: Ha Q /0 H2011: S 03H Yellowish-tiuged red. at Q /CH2CH2S 0311 Red:

OH in a, Q

/CH2CH2 S OaH Red:

/CHzCH2S 03H Red.

CH Red:

/0 HzCHz S 0:13: H CN=N -N=N --N\ & Q

CH3 H CHzCHzS 05 Red;

Construction Shade on perlon CHzCHzS 03H Red.

GHzCHzS 0311 Red.

CHzCHrS H 6GB, (13H:

What is claimed is: 2. Disazo dyestuffs, containing one sulphonic acid 1. Disazo dyestuffs, containing one sulphonic acid group, of the general formula group, of the general formula CHECHPSOaH /CH2CHnSOaH R, R, 1 I GHQ l 2 l N=N- N=N wherein 1) 2 t -Q R R and R independently of one another represent a member selected from the group consisting of methyl and ethyl. wherem 3. Dyestuif of formula R represents chlorine, bromine, methyl, ethyl or tri- CHzCHzSOaH R represents hydrogen or represents a member of the group consisting of chlorine, bromine, methyl, ethyl. E Q methoxy or ethoxy, R represents hydrogen or represents a member of the References Cited group consisting of chlorine, bromine, methyl, ethyl, UNITED STATES PATENTS methmy 2,216,446 10/1940 McNally et al. 260-186 R represents hydrogen or a member of the group consisting of chlorine, bromine, methyl, ethyl, methoxy, 2289413 7/1942 Ems et 260-187 ethoxy and NHCOC H with n representing a LEWIS GOTTS, Primary Examiner number from 0 to 4,

R represents hydrogen or represents a member of the WARREN Asslstant Examiner group consisting of methyl, methoxy and ethoxy, and m represents an integer from 0 to 5 and when m is 25 the members R are the same or different. 260-474, 177. 184, 187, 205, 206, 207.3 

